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Synthesis of Mono- and Diiron Dithiolene Complexes as Hydrogenase Models by Dithiolene Transfer Reactions, Including the Crystal Structure of [{Ni(S2C2Ph2)}6]
Organometallics ( IF 2.5 ) Pub Date : 2019-01-22 , DOI: 10.1021/acs.organomet.8b00852 Harry Adams 1 , Michael J. Morris 1 , Craig C. Robertson 1 , Helen C. I. Tunnicliffe 1
Organometallics ( IF 2.5 ) Pub Date : 2019-01-22 , DOI: 10.1021/acs.organomet.8b00852 Harry Adams 1 , Michael J. Morris 1 , Craig C. Robertson 1 , Helen C. I. Tunnicliffe 1
Affiliation
The dithiolene transfer reaction between the nickel bis(dithiolene) complex [Ni(S2C2Ph2)2] and iron carbonyls has been re-investigated, and the conditions for the production of the dinuclear product [Fe2(μ-S2C2Ph2)(CO)6] have been optimized. Interception of a purple intermediate, thought to be [Fe(CO)3(S2C2Ph2)], in the reaction of [Fe(CO)5] with [Ni(S2C2Ph2)2] by the addition of PPh3 affords the new dark blue mononuclear complex [Fe(CO)2(PPh3)(S2C2Ph2)] in good yield. The fate of the nickel dithiolene fragments in these reactions has also been established by crystallographic characterization of the hexamer [{Ni(S2C2Ph2)}6] and the trinuclear cluster [Ni3(μ-S2C2Ph2)3(PPh3)2]. The substitution reactions of [Fe2(μ-S2C2Ph2)(CO)6] with PPh3 in the presence of Me3NO to give monosubstituted [Fe2(μ-S2C2Ph2)(CO)5(PPh3)] and disubstituted [Fe2(μ-S2C2Ph2)(CO)4(PPh3)2] are also reported.
中文翻译:
包括[{Ni(S 2 C 2 Ph 2)} 6 ]的晶体结构的二硫代烯转移反应作为氢化酶模型合成单-和二铁二硫代烯配合物。
已经对双(二硫代镍)镍配合物[Ni(S 2 C 2 Ph 2)2 ]与羰基铁之间的二硫代转移反应进行了重新研究,并提出了双核产物[Fe 2(μ-S)的生产条件。2 C 2 Ph 2)(CO)6 ]已经过优化。在[Fe(CO)5 ]与[Ni(S 2 C 2 Ph 2)2反应中,拦截为紫色中间体,认为是[Fe(CO)3(S 2 C 2 Ph 2)]通过添加PPh 3可以得到高收率的新型深蓝色单核络合物[Fe(CO)2(PPh 3)(S 2 C 2 Ph 2)]。镍二硫片段在这些反应的命运也已经由六聚体的晶体学表征[{镍(S建立2 c ^ 2博士2)} 6 ]和三核簇[倪3(μ-S 2 c ^ 2博士2)3(PPh 3)2 ]。的取代反应的[Fe 2(μ-S 2c ^ 2博士2)(CO)6 ]与PPH 3在我的存在3 NO,得到单取代的[Fe 2(μ-S 2 c ^ 2博士2)(CO)5(PPH 3)]和二取代的[Fe 2(μ-S 2 c ^ 2博士2)(CO)4(PPH 3)2 ]也报道。
更新日期:2019-02-06
中文翻译:
包括[{Ni(S 2 C 2 Ph 2)} 6 ]的晶体结构的二硫代烯转移反应作为氢化酶模型合成单-和二铁二硫代烯配合物。
已经对双(二硫代镍)镍配合物[Ni(S 2 C 2 Ph 2)2 ]与羰基铁之间的二硫代转移反应进行了重新研究,并提出了双核产物[Fe 2(μ-S)的生产条件。2 C 2 Ph 2)(CO)6 ]已经过优化。在[Fe(CO)5 ]与[Ni(S 2 C 2 Ph 2)2反应中,拦截为紫色中间体,认为是[Fe(CO)3(S 2 C 2 Ph 2)]通过添加PPh 3可以得到高收率的新型深蓝色单核络合物[Fe(CO)2(PPh 3)(S 2 C 2 Ph 2)]。镍二硫片段在这些反应的命运也已经由六聚体的晶体学表征[{镍(S建立2 c ^ 2博士2)} 6 ]和三核簇[倪3(μ-S 2 c ^ 2博士2)3(PPh 3)2 ]。的取代反应的[Fe 2(μ-S 2c ^ 2博士2)(CO)6 ]与PPH 3在我的存在3 NO,得到单取代的[Fe 2(μ-S 2 c ^ 2博士2)(CO)5(PPH 3)]和二取代的[Fe 2(μ-S 2 c ^ 2博士2)(CO)4(PPH 3)2 ]也报道。